JP2003268574A - Rust preventive composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a rust preventive composition which is provided with performances satisfying the quality to be required for rust and working quality for the suspension parts, cap structural parts, plate-clad parts of car bodies, and is harmless for the environment since the quantity of an organic solvent to be volatilized is controlled to ≤10 mass%. <P>SOLUTION: Drying oil having an iodine value of ≥130 in 10 to 60 wt.% to the whole of the composition and specified wax and/or rust preventive additives in 1 to 50 wt.% to the whole of the composition are dissolved with mineral oil based lubricating oil base oils, a synthetic lubricating oil base material or a liquid saturated hydrocarbon mixture, or are dispersed therein. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a rust preventive composition to be applied to vehicles, particularly car body parts, bag structures, etc.
The present invention relates to a rust preventive composition that can be used for long-term rust preventives for general metal materials.

[0002]

2. Description of the Related Art As an anticorrosive agent for underbody parts of a vehicle body, a bag structure part, and a plate bonding part, a composition in which a wax and various additives are dissolved or dispersed in an organic solvent such as mineral spirit, so-called wax Type of rust inhibitor is used. Since these compositions have excellent rust preventive performance, they are also used as long-term rust preventives for metal materials indoors and outdoors.

As a conventional wax type rust preventive, for example, JP-A-60-40159 or JP-A-1-
A composition for improving the film performance as described in JP-A-92267 and a composition for improving the production technology as described in JP-A-61-55198 have been proposed. However, in these compositions,
An organic solvent such as mineral spirit is used as a diluting and dispersing solvent, and a large amount of it contains more than 70% by weight. Therefore, these compositions form a semi-hard wax film by volatilizing the organic solvent into the air after being applied. Since such a volatilized organic solvent has become a problem as one of the causes of recent global warming, studies are underway to reduce the amount of organic solvent used in paints, etc. Then, there is a movement to regulate the amount of volatile organic solvents by law.

[0004]

However, if the organic solvent volatilized from the wax type rust preventive agent is simply reduced, the viscosity increases and sufficient penetration into the gap cannot be obtained. In order to secure the above, the non-volatile content was 80 mass%. In addition, as a method of reducing the organic solvent that volatilizes from the wax type rust preventive agent, a method of substituting a highly viscous oil with low volatility for the organic solvent used in the composition was also examined, but the film after application is forever unsatisfactory. There was a problem that the film could not be sufficiently rust-prevented because the film could fall off due to high temperature or vibration while being dry, or the film could be easily removed by physical force such as contact with water.

Although a method of using a water-based rust preventive composition has been proposed as a method for reducing the amount of organic solvent, in the case of a water-based composition, when it is applied to the bag structure part of the vehicle body and the plate-bonding part, it penetrates There is a problem that the water contained in the composition does not evaporate forever and causes rust. Furthermore, as a method of reducing the organic solvent, a solid wax composition at room temperature is heated and melted at a high temperature for dip coating, or a rust prevention method of pouring the heated and melted wax is also put into practical use, Large-scale equipment is required, and a huge amount of heat energy is required to dissolve the solid wax, which is economically problematic.

Therefore, according to the present invention, the performance of satisfying the rust-prevention required quality and work quality for the underbody parts of the vehicle body, the bag structure part, the plate bonding part, etc.
It is an object of the present invention to provide an environment-friendly rust preventive composition having a mass% or less. Specifically, it is an object of the present invention to provide a rust preventive composition having a low viscosity, a good permeability, an excellent rust preventive property, and capable of forming a dried flexible film after coating.

[0007]

Means for Solving the Problems The present inventors have focused on forming a dry film by an oxidative polymerization reaction caused by exposure to air while the dry oil in oils and fats is a liquid at room temperature. We have succeeded in developing a wax type rust preventive composition that can form a desired flexible film without using a volatile organic solvent by mixing it with an agent or a solvent with low volatility.

Therefore, the rust preventive composition of the present invention contains at least one dry oil selected from fats and oils having an iodine value of 130 or more in an amount of 10 to 60% by weight based on the whole composition, natural waxes and synthetic waxes. At least 1 selected from waxes
Seed waxes and / or sulfonates,
At least one rust preventive additive selected from carboxylic acid salts, fatty acid esters, amine salts, oxidized paraffin salts, and oxidized wax salts is added to the composition in an amount of 1 to 1.
50% by weight with at least one solvent selected from mineral oil-based lubricating base oils, synthetic lubricating oil base materials, liquid saturated hydrocarbon mixtures, vegetable oil-based semi-drying oils and vegetable oil-based non-drying oils It is characterized by being dissolved or dispersed.

Further, in the rust preventive composition of the present invention, the solvent is preferably at least one selected from mineral oil type lubricating base oils, synthetic lubricating oil base materials, and liquid saturated hydrocarbon mixtures. Further, it is preferable that the nonvolatile content at 105 ° C. for 3 hours is 90 mass% or more.

According to the present invention, it is possible to prevent rust for a long period of time like the conventional rust preventive wax containing an organic solvent, and moreover, it can be used in the same manner as the conventional one, and the amount of the volatile organic solvent is small. , Has an excellent effect on global warming countermeasures.
In addition, since the rust-preventive composition of the present invention applies a curing reaction by oxidative polymerization, when applied to a plate-bonding portion such as a bag structure portion, since the inner surface has little contact with air, it never dries. By remaining in the state, it is excellent in followability to the distortion of the vehicle body during traveling, and as a result, a long-term rust preventive effect can be expected. Furthermore, when a conventional solvent-containing wax is used, the wax adhering to the coated surface contaminates the coating, so it was necessary to quickly remove the wax adhering during transportation or assembly. Since the rust preventive composition does not use a solvent, it has no stains on the coating, and the wiping operation can be omitted.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION The rust preventive composition of the present invention will be described in more detail below. The drying oil in the present invention is an oil or fat having an iodine value of 130 or more, and specifically,
Examples include linseed oil, eno oil, tung oil, hemp oil, safflower oil, deer oil, sardine oil, herring oil, castor oil, dehydrated castor oil, which is a conjugate acid, and synthetic drying oil. Among these, it is preferable to use linseed oil, tung oil, and dehydrated castor oil, which are easily available, alone or in a mixture, and it is more preferable that the amount of dehydrated castor oil is large. In the present invention, the blending amount of the drying oil is in the range of 10 to 60% by weight, preferably 30 to 40% by weight, based on the whole composition. If this blending amount is less than 10%, the film of the rust preventive composition cannot obtain sufficient dryness, resulting in a non-drying film, which is not preferable. On the other hand, this blend amount is 60
When the content is more than 0.1%, the coating film after drying of the rust preventive composition is too hard, and excellent corrosion resistance performance due to the flexible film, which is an advantage of the rust preventive wax, cannot be obtained.

The waxes in the present invention include natural waxes such as candelilla wax, carnauba wax, rice wax, wood wax, jojoba oil, and other vegetable oil waxes, and beeswax, lanolin, whale wax, and other animal waxes. In addition, mineral oil waxes such as montan wax, ozokerite and ceresin, and petroleum waxes such as paraffin wax, microcrystalline wax, petrolatum and the like can be mentioned.

Examples of synthetic waxes include synthetic hydrocarbons such as Fischer-Tropsch wax and polyethylene wax, modified waxes such as montan wax derivatives, paraffin wax derivatives and microcrystalline wax derivatives, hydrogenated waxes such as hardened castor oil and hardened castor oil derivatives, Fatty acids such as 12-hydroxystearic acid,
Examples thereof include acid amides such as stearic acid amide, esters such as phthalic anhydride imide, chlorinated hydrocarbons, and compounded waxes prepared by mixing these. These waxes can be blended alone or in a mixture, and the melting point of the wax used is preferably 60 ° C or higher and lower than 130 ° C, more preferably 80 to 100 ° C. If this melting point is lower than 60 ° C., when applied to the inner surface of the vehicle body, it melts and is sagging when exposed to the high temperature in summer before the dry operation. On the other hand, if the melting point is higher than 130 ° C, a high temperature is required during the production of the composition, which is not practical.

Specifically, paraffin wax, microcrystalline wax, petrolatum, polyethylene wax, and various modified waxes are preferably blended alone or in combination. More preferably, microcrystalline wax is used alone or in a mixture.

Further, in the present invention, sulfonates, carboxylates, fatty acid esters, amine salts,
Even if a rust preventive additive selected from oxidized paraffin salts and oxidized wax salts is used instead of the above waxes, the same effect as the waxes can be obtained. Although some of the rust preventive additives have been diluted with an organic solvent in advance, it is preferable that the rust preventive additives to be blended in the present invention have the least volatile components. Specifically, oil-cut sulfonates, fatty acid esters, oxidized paraffin salts and the like are preferable. More preferably, the oil-cut Ca sulfonic acid salt and the fatty acid ester are used alone or in a mixture.

In the present invention, excellent corrosion resistance can be obtained by adding a wax or an anticorrosive additive to impart water repellency to the film and at the same time forming a dense continuous film. Further, it becomes possible to adjust the viscosity by utilizing the crystallization effect of the wax. The amount of the waxes and rust-preventive additives used in the present invention is 1 to 50% by weight, preferably 10 to 30%, based on the total composition.
% By weight. It should be noted that a relatively small amount is preferable when a highly crystalline substance is added, and conversely, a large amount is preferable when a low crystalline substance is added. If the blending amount is less than 1% by weight, sufficient corrosion resistance cannot be obtained. On the other hand, if the blending amount exceeds 50% by weight, the viscosity becomes too high, the workability is poor, and uniform coating is difficult.

The solvent in the present invention is for dissolving or dispersing each component to adjust the viscosity to a purpose, and is a mineral oil type lubricating base oil, a synthetic lubricating oil base material, a liquid saturated hydrocarbon. It is selected from mixtures, vegetable oil-based semi-drying oils and vegetable oil-based non-drying oils. Specifically, paraffinic lubricating base oils, naphthenic lubricating base oils and the like are used as mineral lubricating base oils, and ester-based lubricating base oils are used as synthetic lubricating bases.
Polyalpha olefin type, polyalkylene glycol type, polybutene type, alkyl diphenyl ether type, etc., liquid saturated hydrocarbon mixture, liquid paraffin, vegetable oil type semi-drying oil, soybean oil, cottonseed oil, rapeseed oil, rice oil , Sesame oil, sunflower oil, corn oil and the like, and vegetable oil-based non-drying oils include olive oil, peanut oil, camellia oil and the like, which can be used alone or in combination.

Since the solvents for the vegetable oil type semi-drying oils and the vegetable oil type non-drying oils contain many double bonds in the molecule, in consideration of long-term stability, mineral oil type lubricating base oils are used. ,
Synthetic lubricating oil base stocks or liquid saturated hydrocarbon mixtures are preferred. Further, in the present invention, those having a low volatility are preferable, and specifically, those having a volatilization amount at 105 ° C. for 3 hours of 5% by weight or less are preferable, and further, the volatilization amount at 105 ° C. for 3 hours is 1% by weight. The following are more preferable.

Further, the rust preventive composition of the present invention contains pigments and fillers for the purpose of adjusting the film hardness within a range satisfying the required quality and improving the sag property by providing thixotropy. It is also possible to mix a kind. Examples of the pigment to be blended include red iron oxide, zinc dust, zinc phosphate, and the like, and various conventionally known pigments can also be used. Examples of the filler include calcium carbonates, kaolin clays, talcs, mica, bentonites, and various conventionally known extender pigments. Further, if necessary, a coloring pigment such as carbon black or titanium oxide may be added in an appropriate amount to give an arbitrary color.

Further, the rust preventive composition of the present invention may be added with a curing accelerator for the purpose of improving and controlling the drying rate, and an anti-skinning agent for the purpose of preventing surface curing. Examples of the curing accelerator include cobalt naphthenate, manganese naphthenate, and various conventionally known additives. Further, examples of the anti-skinning agent include butylated hydroxytoluene and various conventionally known additives.

The anticorrosive composition of the present invention is applied to the underbody parts of the vehicle body, the bag, by spray coating with a conventionally known coating machine such as airless spray, air spray, flow coating in a shower state, direct coating with a brush or the like. It is possible to form a rust preventive film having excellent performance on the structure part, the plate-bonding part, and the like. In the case of long-term rust prevention, the applied film thickness is preferably 30 μm or more.

[0022]

EXAMPLES The present invention will be described in more detail with reference to specific examples and comparative examples. The present invention is not limited to the examples below. 1. Preparation of Anticorrosion Composition <Example 1> The raw materials having the formulations shown in Table 1 were mixed and then heated and dissolved. Next, this was thoroughly stirred with a stirrer and then cooled to prepare the rust preventive composition of Example 1 of the present invention. In Tables 1 and 2, microcrystalline wax is a commercially available product having a melting point of 87 ° C., calcium sulfonate is an oil cut product of a basic alkylbenzene calcium salt, fatty acid ester is glycerin oleate, and paraffinic lubricant base oil is generally used. Commercially available 500 neutral oil, liquid paraffin has a kinematic viscosity of 70 at 40 ° C.
mm ² / s generally commercially available and the calcium carbonate particle size 0.
1 μm, bentonite having an average particle size of 3 μm dispersed in a solvent in advance, and other raw materials were commercially available products.

<Examples 2 to 16 and Comparative Examples 1 to 7> Except that the ingredients were changed to those shown in Tables 1 and 2.
In the same manner as in Example 1, the rust preventive compositions of Examples 2 to 16 of the present invention and the rust preventive compositions of Comparative Examples 1 to 7 were prepared.

[0024]

[Table 1]

[0025]

[Table 2]

<Comparative Examples 8 to 10> A conventional rust preventive wax, NOX-RUST HS manufactured by Parker Kosan Co., Ltd.
-700 (trade name) was used as the rust preventive composition of Comparative Example 8. Moreover, NOX-RUST 117 (trade name) manufactured by Parker Kosan Co., Ltd., which is a conventional high solid content rust preventive wax.
Was used as the rust preventive composition of Comparative Example 9. Further, the solvent of NOX-RUST HS-700 (trade name) of Comparative Example 8 was changed to a lubricating oil, which was used as a rust preventive composition of Comparative Example 10.

2. Evaluation Test The rust preventive compositions of the respective Examples and Comparative Examples prepared as described above were tested by the method described below to evaluate the performance. The results of these evaluations are shown in Tables 3 and 4.

(1) Anticorrosion performance (salt spray test) 70 × 150 × 0.8 dried by removing oil with a solvent
mm of cold rolled steel sheet (JISG3141SPCC-SD) was coated with a rust preventive composition of each Example and Comparative Example to a film thickness of 30 μm using a bar coater, dried at room temperature for 1 week, and then sprayed with salt water for 360 hours. The test was conducted. In this test, the appearance of each steel sheet was observed and the time until rusting was measured. If the rusting time was 240 hours or more, ◎, 12
The rust preventive performance was evaluated by assigning 0 to 240 hours as O, 48 to 119 hours as Δ, and 48 hours or less to X.

(2) Film state after drying Oil was removed with a solvent and dried 70 × 150 × 0.8
mm of cold rolled steel sheet (JISG3141SPCC-SD) was applied with a bar coater to the rust preventive composition of each Example and Comparative Example to a film thickness of 30 μm, dried at room temperature for 1 week, and then touched with a finger. The film was evaluated for stickiness and film hardness. As for the evaluation criteria, with regard to stickiness, those without stickiness are ○, those with stickiness are △,
If there is a lot of stickiness and sticks to the finger, it is marked as X, and as for hardness, if the film is a soft film and has good flexibility, it is ○, if the film is too hard and too hard or too soft. It was set to x.

(3) Penetration Two 70 × 150 × 0.8 mm cold-rolled steel sheets (JISG3141SPCC-SD) whose ends were bent at an angle of 30 degrees at a position of 50 mm from one end in the lengthwise direction were prepared, After removing these oil components with a solvent and drying, these steel plates were laminated so that the surfaces opposite to the side where the ends were bent were opposed to each other so that their cross sections were Y-shaped. At this time, a Teflon (registered trademark) spacer having a thickness of 100 μm was sandwiched between both ends in the width direction. Then, these were fixed with clips to form a jig for evaluating permeability. This jig was set up with the bent part facing up, 1 ml of the rust preventive composition of each Example and Comparative Example was injected from the upper part into the gap between the steel plates sandwiched by the spacers using a dropper, and the mixture was left for 24 hours. , Disassemble the jig and measure the permeation length.
mm is more than ◯, 29mm or less is x,
The permeability was evaluated. The test atmosphere, the jig and the rust preventive composition were all adjusted to a temperature of 10 ° C.

(4) Oil was removed with a heat-resistant sagging solvent and dried to 70 × 150 × 0.8.
mm cold-rolled steel sheet (JISG3141SPCC-SD) was masked on the lower half surface and the upper half surface was coated with a rust preventive composition of each Example and Comparative Example using a bar coater at 200 μm.
After leaving for 1 week at room temperature, remove the masking and leave it in a dryer at 80 ° C for 1 hour vertically, measure the sag of each rust preventive composition, and measure the length of sag Is 10m
m or less ○, 11 to 50 mm △, 51 m
The heat sag resistance was evaluated by setting x as m or more.

(5) Coating workability The rust preventive compositions of Examples and Comparative Examples were adjusted to a liquid temperature of 20 ° C., and the discharge pressure was 4.9 M using an airless pump for coating.
Spray on a chip with a Pa diameter of 15/100 inch,
The dischargeability was observed, and the coating workability was evaluated by ◯ when the discharge state was uniformly atomized, Δ when the discharge state was slightly uneven, and X when the discharge state was uneven and uneven.

(6) Coating Contamination A rust preventive composition of each Example and Comparative Example was dropped by 0.1 ml onto a coated plate which had been subjected to a top coat for automobiles, and was horizontally placed in a dryer at 60 ° C. After leaving it for 1 hour, it was cooled at room temperature for 30 minutes. Then, each rust preventive composition was lightly wiped and removed with a gauze moistened with a solvent, and then those having no discoloration and swelling were evaluated as ◯, those having swelling as Δ, and those having discoloration as × were evaluated for stain resistance.

(7) Drying time The oil content was removed with a solvent and dried to 70 × 150 × 0.8.
mm cold-rolled steel sheet (JISG3141SPCC-SD) using a bar coater to apply the rust preventive composition of each Example and Comparative Example to a film thickness of 30 μm, and leave it indoors at room temperature,
The film was evaluated for the drying time by touching the film with a finger on the dry state depending on the elapsed time, ◯ when the dry operation time was within 24 hours, Δ when the dry operation time was within 1 week, and x when not dried.

(8) Nonvolatile content 4. According to JIS K5407. The non-volatile components of the rust preventive compositions of Examples and Comparative Examples were measured according to the test method for heating residue in the coating composition test method, and the heating residue having a heating residue of 99% or more was evaluated as ○, and the heating residue of 90% or more was evaluated as Δ. , 89% or less was evaluated as x, and the nonvolatile content was evaluated.

[0036]

[Table 3]

[0037]

[Table 4]

As shown in Tables 3 and 4, the rust-preventing compositions of Examples 1 to 16 of the present invention showed excellent performance in practical use without any problems in all items. With respect to the rust preventive compositions of 8 to 10, a rating of O or higher was obtained in all items, and it was shown to be extremely effective as an environment-friendly rust preventive wax composition. On the other hand, Comparative Example 1 in which the amount of the drying oil is too small
In Nos. 1 and 2, anticorrosion performance, film state after drying, heat dripping resistance, and drying time were inferior, while too much Comparative Examples 3 and 4
Then, there was a problem in rust prevention performance and film hardness after drying. Further, in Comparative Example 5 in which the wax and / or the anticorrosive additive is too small, sufficient anticorrosive performance cannot be obtained, while
In Comparative Examples 6 and 7 which were too much, the penetrability and the coating workability were poor. Further, the rust preventive composition of the present invention is capable of long-term rust preventive as in the case of Comparative Examples 8 and 9 which are rust preventive waxes containing a conventional organic solvent, and can be used in the same manner as the conventional method. Nevertheless, it has been shown that the composition is an excellent environment-friendly rust preventive composition which has a small amount of volatile organic solvent and is effective for global warming countermeasures. Further, in the present invention, it was also shown that it is possible to prepare a characteristic rust preventive composition by varying the compounding amounts of the drying oil and the wax and / or the rust preventive additive.

[0039]

As described above, at least one drying oil selected from fats and oils having an iodine value of 130 or more is contained in an amount of 10 to 60% by weight based on the whole composition, and natural waxes and synthetic waxes are used. At least one wax selected and / or at least one rust preventive additive selected from sulfonates, carboxylates, fatty acid esters, amine salts, oxidized paraffin salts, and oxidized wax salts 1 to 50% by weight based on the total composition, mineral oil-based lubricating base oils, synthetic lubricating base oils, liquid saturated hydrocarbon mixtures, vegetable oil-based semi-drying oils and vegetable oil-based non-drying oils By dissolving or dispersing with at least one solvent selected from among the following, it is possible to satisfy the requirements for rust prevention and work quality for the underbody parts of the vehicle body, the bag structure part, the plate matching part, etc. Provided, the organic solvent volatilizes 10
An environment-friendly rust preventive composition having a mass% or less can be obtained. Further, in comparison with the conventional solvent-containing type rust preventive wax that cannot be expanded and used due to solvent regulations, the rust preventive composition of the present invention can sufficiently meet the increasingly strict requirements for automobile rust preventiveness in recent years. At the same time, it is a very effective means in terms of cost.

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Toshihiro Takeuchi             1-4-1 Chuo 1-4-1 Wako City, Saitama Prefecture             Inside Honda Research Laboratory (72) Inventor Shinji Takehara             1-4-1 Chuo 1-4-1 Wako City, Saitama Prefecture             Inside Honda Research Laboratory F-term (reference) 4K062 AA01 BA08 BB01 BB03 BB09                       BB12 BB30 BC01 BC07 BC13                       BC14 BC30 CA05 CA08 FA03                       FA12 GA01 GA08

Claims (3)

[Claims] 1. At least one dry oil selected from fats and oils having an iodine value of 130 or more is used in an amount of 10 to 10 with respect to the entire composition.
60% by weight of at least one wax selected from natural waxes and synthetic waxes, and / or sulfonates, carboxylates, fatty acid esters, amine salts, oxidized paraffin salts, and oxidized wax salts. 1 to 50% by weight of at least one rust preventive additive selected from the above, based on the total composition, mineral oil-based lubricating base oil, synthetic lubricating oil base material, liquid saturated hydrocarbon mixture, A rust preventive composition characterized by being dissolved or dispersed in at least one solvent selected from vegetable oil semi-drying oils and vegetable oil non-drying oils. 2. The protective agent according to claim 1, wherein the solvent is at least one selected from mineral oil-based lubricating base oils, synthetic lubricating oil base materials, and liquid saturated hydrocarbon mixtures. Rust composition. 3. The nonvolatile content at 105 ° C. for 3 hours is 9
The rust preventive composition according to claim 1 or 2, wherein the content is 0 mass% or more.